- PROCESSES FOR FLUORINATION
-
The present technology relates to fluorination reactions. Specifically, processes useful for making the fungicide compound, DFT are disclosed. More broadly, also disclosed herein are processes useful for deoxyfluorination at the α-aromatic position of a given compound.
- -
-
Paragraph 0179; 0184; 0214-0215; 0218
(2021/04/10)
-
- PROCESSES FOR FLUORINATION
-
The present technology relates to fluorination reactions. Specifically, processes useful for making the fungicide compound, DFT are disclosed. More broadly, also disclosed herein are processes useful for deoxyfluorination at the α-aromatic position of a given compound.
- -
-
Paragraph 0188
(2020/03/05)
-
- Thiourea-Catalyzed C?F Bond Activation: Amination of Benzylic Fluorides
-
We describe the first thiourea-catalyzed C?F bond activation. The use of a thiourea catalyst and Ti(OiPr)4 as a fluoride scavenger allows the amination of benzylic fluorides to proceed in moderate to excellent yields. Preliminary results with S- and O-based nucleophiles are also presented. DFT calculations reveal the importance of hydrogen bonds between the catalyst and the fluorine atom of the substrate to lower the activation energy during the transition state.
- Houle, Camille,Savoie, Paul R.,Davies, Clotilde,Jardel, Damien,Champagne, Pier Alexandre,Bibal, Brigitte,Paquin, Jean-Fran?ois
-
supporting information
p. 10620 - 10625
(2020/07/24)
-
- Cobalt-Catalyzed Asymmetric Cross-Coupling Reaction of Fluorinated Secondary Benzyl Bromides with Lithium Aryl Boronates/ZnBr2
-
A cobalt-catalyzed asymmetric cross-coupling of α-bromo-α-fluorotoluene derivatives with a variety of aryl zincates derived from lithium aryl n-butyl pinacol boronates and ZnBr2 under mild reaction conditions was described. In addition to mild reaction conditions, another advantage includes the compatibility of various common functional groups such as fluoride, chloride, bromide, cyano, or ester groups. Furthermore, this protocol was successfully applied to the enantioselective synthesis of three fluorinated derivatives of biologically active compounds or drug molecules.
- Huang, Weichen,Shen, Qilong,Wan, Xiaolong
-
supporting information
p. 4327 - 4332
(2020/06/27)
-
- Expanding the repertoire of cyclopropenium ion phase transfer catalysis: Benzylic fluorination
-
The application of cyclopropenium ion as a phase transfer catalyst for benzylic fluorination in high yields is reported. Integral to the mechanisms of these fluorination reactions was the role of in situ derived cyclopropenium fluoride complexes, the existence of which was supported by 1H, 19F NMR and UV–Vis spectroscopy. Density functional theory calculations were applied to gain insight into the mechanism of these reactions.
- Dempsey, Katie,Mir, Roya,Smajlagic, Ivor,Dudding, Travis
-
p. 3507 - 3511
(2018/05/25)
-
- Friedel-crafts reaction of benzyl fluorides: Selective activation of C-f bonds as enabled by hydrogen bonding
-
A Friedel-Crafts benzylation of arenes with benzyl fluorides has been developed. The reaction produces 1,1-diaryl alkanes in good yield under mild conditions without the need for a transition metal or a strong Lewis acid. A mechanism involving activation of the C-F bond through hydrogen bonding is proposed. This mode of activation enables the selective reaction of benzylic C-F bonds in the presence of other benzylic leaving groups.
- Champagne, Pier Alexandre,Benhassine, Yasmine,Desroches, Justine,Paquin, Jean-Franois
-
supporting information
p. 13835 - 13839
(2015/02/05)
-
- An easy access to fluoroalkanes by deoxygenative hydrofluorination of carbonyl compounds via their tosylhydrazones
-
An efficient and operationally simple synthesis of fluoroalkanes by deoxygenative hydrofluorination of carbonyl compounds via their tosylhydrazone surrogates is reported. The reaction can be carried out in a one-pot procedure directly from carbonyl compounds.
- Yadav, Arvind K.,Srivastava, Vishnu P.,Yadav, Lal Dhar S.
-
supporting information
p. 2154 - 2156
(2013/03/14)
-
- Electrochemical fluorination using halogen mediators in ionic liquid hydrogen fluoride salt
-
In order to utilize ammomium halides (Et4NX, X=Cl, Br, I) as halogenmediator for electrocatalytic fluorination, cyclic voltammetry measurements of the halides were investigated. The catalytic current of the halides in the presence of a dithioacatal compound was observed and the macro-scale electrolysis of dithioacetals using the halogen mediator was also carried out in ionic liquid hydrogen fluoride (HF) salt to give the corresponding fluorinated products in excellent yields. The recycle use of the halogen mediator in the electrochemical fluorination was successfully demonstrated. More inexpensive halides such as potassium bromide and potassium iodide could be soluble in HF salt and worked well as halogen mediator for the electrocatalytic fluorination.
- Takahashi, Kohta,Inagi, Shinsuke,Fuchigami, Toshio
-
p. G3046-G3052
(2013/07/05)
-
- Palladium-catalyzed substitution and cross-coupling of benzylic fluorides
-
Benzylic fluorides are suitable substrates for Pd(0)-catalyzed Tsuji-Trost substitution using carbon, nitrogen, oxygen, and sulfur nucleophiles and for cross-coupling with phenylboronic acid. For the bifunctional substrate 4-chlorobenzyl fluoride, fine-tuning of the reaction conditions allows for the regioselective displacement of either the chlorine or fluorine substituent. The leaving group ability of fluoride vs other groups displaced in substitution is CF3CO2 ≈ p-NO2C6H 4CO2 ≈ OCO2CH3 > F > CH3CO2, a ranking similar to allylic fluorides under Pd catalysis.
- Blessley, George,Holden, Patrick,Walker, Matthew,Brown, John M.,Gouverneur, Veronique
-
supporting information; experimental part
p. 2754 - 2757
(2012/07/16)
-
- Recyclable polymer-supported iodobenzene-mediated electrocatalytic fluorination in ionic liquid
-
The electrochemical fluorination of organosulfur compounds in triethylamine/hydrofluoric acid (Et3N-5HF) with polystyrene-supported iodobenzene (PSIB) and tetraethylammonium chloride (Et4NCl) was performed successfully in an undivided cell under constant current conditions to afford the corresponding fluorinated compounds in moderate to good yields. Recycle use of the PSIB could be achieved due to its easy separation. Notably, the mediatory activity of the iodobenzene derivative was not appreciably changed even after 10 recycle uses.
- Sawamura, Takahiro,Kuribayashi, Shunsuke,Inagi, Shinsuke,Fuchigami, Toshio
-
experimental part
p. 2757 - 2760
(2010/12/25)
-
- Practical and general method for direct synthesis of alkyl fluorides from alcohols under mild conditions
-
A variety of alcohols were treated with Ph 3P and KF in CCl 4-DMF at room temperature to afford the corresponding fluorides in very good yields. Springer-Verlag 2005.
- Bandgar, Babasaheb P.,Kamble, Vinod T.,Biradar, Ankush V.
-
p. 1579 - 1582
(2007/10/03)
-
- Efficient and selective halogenation of allylic and benzylic alcohols under mild conditions
-
A simple, mild, and high yielding procedure for the halogenation of allylic and benzylic alcohols using a combination of SOCl2, benzotriazole, and potassium halides in DMF is described. The effectiveness of the protocol is manifested in its selectivity towards allylic and benzylic alcohols whereas other simple alcohols such as primary, secondary, and tertiary are found to be unreactive. Springer-Verlag 2004.
- Bandgar, Babasaheb P.,Bettigeri, Sampada V.
-
p. 1251 - 1255
(2007/10/03)
-
- Process for the production of fluorinated organic compounds and fluorinating agents
-
A process for the production of a fluorinated organic compound, characterized by fluorinating an organic compound having a hydrogen atoms using IF5; and a novel fluorination process for fluorinating an organic compound having a hydrogen atoms by using a fluorinating agent containing IF5 and at least one member selected from the group consisting of acids, bases, salts and additives.
- -
-
-
- Novel fluorination reagent: IF5/Et3N-3HF
-
IF5 in Et3N-3HF was found to be a stable, non-hazardous, easy to handle, and inexpensive reagent that enables effective and selective fluorination of organic compounds under mild conditions.
- Yoneda, Norihiko,Fukuhara, Tsuyoshi
-
p. 222 - 223
(2007/10/03)
-
- Novel Synthesis of 2,2,2-Trifluoroethyl Compounds from Homoallylic Alcohols: A Copper(I) Iodide-initiated Trifluoromethyl-Dehydroxylation Process
-
Benzyl, prop-2-enyl and allyl chlorodifluoroacetates 3a, bromodifluoroacetates 3b or fluorosulfonyldifluoroacetates 3c, when decomposed in the presence of 1 equivalent of copper(I) iodide at an appropriate temperature in dimethylformamide, gave the corresponding trifluoromethyl derivatives in good to excellent yields.The products can also be obtained directly by ester exchange of XCF2CO2Et (X = FSO2, Cl, Br) 6 and the corresponding alcohols in the presence of KF and CuI.A trifluoromethylation-dehydroxylation mechanism, initiated by CuI, is proposed.
- Duan, Jian-Xing,Chen, Quing-Yun
-
p. 725 - 730
(2007/10/02)
-
- Substituent modulation of mild fluorination of aromatic molecules with caesium fluoroxysulphate
-
Functionalization of mono- and di-substituted benzene derivative with CsSO4F has been modulated by substituents on the benzene ring. α-Hydroxyalkylbenzenes, with a deactivated ring, were oxidized to phenones, while fluorodealkylation was achieved in high yield when electron-donating groups were present in a para position. Electron-withdrawing substituents favoured chain fluorofunctionalization in alkylbenzenes, while ring fluorination was found exclusively in acylamino-derivatized alkylbenzenes; fluoro-addition products were formed in the case of p-alkoxy-substituted alkylbenzene derivatives.
- Stavber, Stojan,Planinsek, Zdenka,Kosir, Iztok,Zupan, Marko
-
p. 409 - 412
(2007/10/02)
-
- MECHANISMS OF FREE-RADICAL REACTIONS. XX. REACTIVITY IN THE FREE-RADICAL HALOGENATION REACTIONS OF ARYLFLUOROALKANES
-
The free-radical chlorination and bromination of meta- and para-substituted benzyl fluorides and 1,1-difluoro-2-phenylethane and also the chlorination of 1-fluoro-2-arylethanes by phenylchloroiodonium chloride and the bromination of meta- and para-substituted benzyl bromides were studied by the method of competing reactions.In all cases a good correlation is observed between log krel and the Brown ?+ constants.In cases where change in the reactivity in the transition from one reaction series to another is due mainly to the polar effect of the substituent whilethe selectivity is measured in relation to the polar effect direct relationships are observed between the reactivity and the selectivity.
- Dneprovskii, A. S.,Eliseenkov, E. V.
-
p. 711 - 719
(2007/10/02)
-
- A Facile Method for the Fluorine Substitution of Phenylthio Group via Sulfonium Salts Using Cesium Fluoride
-
Monofluorinated compounds are easily prepared in good yields by treating phenyl sulfides with methyl fluorosulfonate and cesium fluoride in refluxing dichloromethane, successively.This reaction proceeds under so mild conditions as not to affect the coexisting bromine substituent.
- Ichikawa, Junji,Sugimoto, Ken-ichi,Sonoda, Takaaki,Kobayashi, Hiroshi
-
p. 1985 - 1988
(2007/10/02)
-
- Selective Fluorination of Substituted Methanols with Methanesulfonyl Fluoride and Cesium Fluoride as Modified with Crown Ethers
-
A new combination of methanesulfonyl fluoride and cesium fluoride as modified with 18-crown-6 was demonstrated to be the best for selective fluorination of various benzyl alcohols via nucleophilic substitution.As extended applications of this procedure, ethyl 1-fluoromethylpyrazole-4-carboxylate (6) and N-fluoromethylphthalimide (12) have been synthesized in high yields from the corresponding alcohol (4) and chloride (11) respectively.
- Makio, K.,Yoshioka, H.
-
p. 677 - 684
(2007/10/02)
-
- The Combination of Potassium Fluoride and Calcium Fluoride: A Useful Heterogeneous Fluorinating Reagent
-
The combination of potassium fluoride and calcium fluoride was found to be an effective and practical solid reagent for the fluorination of various organic chlorides and bromides under mild conditions.
- Ichihara, Junko,Matsuo, Toshiya,Hanafusa, Terukiyo,Ando, Takashi
-
p. 793 - 794
(2007/10/02)
-
- FLUORINATION OF HALOGENO ALCOHOLS WITH 1,1,2,3,3,3-HEXAFLUOROPROPYL DIETHYLAMINE
-
Fluorination of halogeno alcohols with 1,1,2,3,3,3-hexafluoropropyl diethylamine (PPDA) was investigated. 2-Bromo-1-fluorobutane was obtained from the reaction of PPDA and 2-bromo-1-butanol (yield 50percent).Similar results were obtained from other alipha
- Watanabe, S.,Fujita, T.,Usui, Y.,Kimura, Y.
-
p. 135 - 142
(2007/10/02)
-
- The Preparation of Primary Alkyl and Benzyl Fluorides from the Corresponding Primary Amines
-
N-substituted 2,4,6-triphenylpyridinium fluorides (in contrast to these and other tetrafluoroborates) thermolyse to the corresponding primary alkyl and benzyl fluorides.The pyridinium fluorides are made from 2,4,6-triphenylpyrylium fluoride and the relevant amine.
- Katritzky, Alan R.,Patel, Ranjan C.
-
p. 2901 - 2903
(2007/10/02)
-
- ACTION DU METHYLTRI(N-BUTYL)FLUOROPHOSPHORANE SUR LES HALOGENURES ET LES SULFONATES D'ALKYLE
-
Monofluorophosphoranes R3MePF are used in exchange reactions to prepare monofluorinated organic compounds.Tri(n-butyl)methylfluorophosphorane (n-Bu3MePF), easily available, is the most reactive.In solvents of low polarity or even in non-polar solvents, it reacts at -70 deg C with alkyl sulphonates and halides activated by ester, ketone, or ether functions.Thus, fluorinated epoxides can be obtained directly by exchange from their chlorinated or brominated homologues.
- Leroy, J.,Bensoam, J.,Humiliere, M.,Wakselman, C.,Mathey, F.
-
p. 1931 - 1936
(2007/10/02)
-